Leuco sulfuric acid esters of trianthrimide carbazole dyestuffs and method for producing the same



Patented July 22, 1952 LEUCO SULFURZICIACID ESTERS oF Tm ANTHRIMIDE VCARBAZOLE DYESTUFFS AND METHOD FOR, PRODUCING THE SAME Samuel Coffey, David Alexander Whyte Fairweather, and Frank Hayhurst Slinger, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application November 18, 1947, Se

rial No. 786,795. 25, 1946 This invention relates to, a new dyestuff and in particular it relates to a process for themanu- 'facture of anew leuco sulphuric ester derivative of 1:l :5:1" trianthrimicle-2z2':6:2"'-carbazole.

It has been proposed to make. sulphuric esters of leuco derivativesof vat dyestufis byptreating the leuco derivative of the vat dyestufi with for example chlorosulphonic acid in the presence of a tertiary base for example pyridine or by treating the vat dyestufi itself in tertiary base suspension in the presence of a metal with sulphur 'trioxide or with a substance which can give rise to sulphur trioxide in 'the' reaction mixture. Also in British specification No. 274,156 it was proposed to react the vat dyestufi in tertiary base suspension with the metal'before the addition of sulphur trioxide, and a process was described for the manufacture of derivatives of vat dyestuffs by reacting a' quaternary ammonium halide which may be obtained by the reaction between a tertiary organic base and an alkyl halide, in tertiary organic base suspension, with a metal, reacting the product with a vat 'dyestuff, and then reacting the resulting mixture with the, product obtained by the interaction of a tertiary base with a reagent adapted to yield the sulphuric anhydride compound of the tertiary base, for example an allcyl 'chlorsulphonate, chlorsulphonic acid, oleum or sulphur trioxide; Pyridine and dimethylaniline were mentioned as examples of bases which could be used in the process. A

It is known however that leuco sulphuric esters obtained by hitherto known processes from vat dyestufis of the anthrimide carbazoles series are in general unsuitable for dyeing and printing since the shades obtained are dull and weak, have poor fastness properties and are different in hue from those obtained by the normal vat dyeing processes with the parent anthrimide carbazole.

We have found however that the above-mentioned trianthrimide carbazole, the leuco sulphuric ester derivative of which has not hitherto been described can be satisfactorily converted into a leuco sulphuric ester derivative when instead of using pyridine or other tertiary base in the above processes there is used an organic amide as hereinafter defined and we have further found that the leuco sulphuric ester so ob- 3 Claims. (01. 2e0 16) toluenesulphonamide. ample acetone and acetonitrile may also be added to the reaction mixture. 1

I ,The formation of the leuco sulphuric ester may be carried out by treating the carbazole in the In Great Britain November Y,

tained is suitable for use in dyeing and printing and gives shades similar in properties to those obtained with the parent vat 'dyestuff by the normal vat dyeing process.

, According to our invention therefore we provide a" process for the manufacture of the new leuco sulphuric ester derivative of l:l:5:1"'-trianthrimide-2 2' :6 :2 '-carbazole characterised in that the formation of the leuco sulphuric ester is carriedout in the presence of an organic amide in which the hydrogen atoms attached to the amide nitrogen atom have been replaced by hydrocarbon radicles or substituted hydrocarbon radicles. h

;As examples of suitable amides for use in the reaction there may be'mentioned amides derived from carboxylic acids, for example dimethylformamide, diethylformamide, dimethylacetamide, tetramethylurea and amides derived from sulphonic acids, for example NzN-diethyl-p- Diluents such as for expresence of the organic amide and a metal for example zinc, copper and iron with sulphur trioxide or with the'addition compound of suliphur trioxide and an'organicamide or tertiary base or with any knownsubstan'ce for forming sulphuric esters from vat dyestufis in the presence of metals or from leuco compounds or metal salts thereof or complex compounds comprising the metal salts thereof. By a known substance we mean a substance actually used for this purpose or whose use is disclosed in the literature on the subject.

Alternatively instead of the carbazole itself and a metal there may be used a metal salt of the corresponding leuco compound. In general it is preferred to use the metal salt of the corresponding leuco compound or the complex compound comprising the metal salt of the corresponding leuco compound which may be made for example by reacting the parent vat dyestuff with a metal, for example zinc, in the presence of an organic amide as hereinbefore defined and preferably in the presence of a small quantity of a salt for example potassium methyl sulphate.

The leuco sulphuric ester salt so obtained may 6.46 parts of fine state of division, to a vigorously stirred mixture of 50 parts of dimethyl formamide, 6 parts of zinc dust and 0.6 part of potassium ethyl sultrianthrimide-. 2:2:6:2"-carbazole which may bemade by ring.- closing 1:1'-5:1"-trianthrimide is added, in aphate. A current of nitrogen is passed through the reaction vessel and the mixture is stirred'fo'r /z-hour at C. The mixture is then cooled 'in an ice bath and the product obtained by reacting together 23.5 parts of methylchlorosulphonat'e and 35 parts of dimethyl'formamide is added. The colour of the reaction mixture changes from red-brown to yellow. The mixture is stirred for;

a further /2 hour and then poured. into an excess of 5% sodium carbonate solution. Theprecipi- 'tated zinc carbonate is removed by filtration.

with 3.5 parts of dextrin anddried in vacuo.

Theproduct can be applied to fabrics in the usual manner and gives yellow shades of good fastness.

. Example 2 6.46 parts of 1:1':5:1." trianthrimide- 2;:2":6:2;-carbazo1e is added to a vigorously stirred. mixture. of parts of dimethylformamide, 6 parts of zinc dust and 0.6 partor'sodium fi-naphthol' sulphonate. Nitrogeniis passed through the vessel and .themixture is'stirred for l-"hour' at 0 C. The resulting red-brown solution is added to the product obtained by reacting together 23.5 parts of methyl chlorosulphonate andi parts of dimethylformamide which is stirred in an icebath durin'g"the addition. The mixture is stirred for a further 5 hour'an'd the product is then isolated as described in Example 1.

E:z:zz.1vz.ple3

3.23v parts of 1:I':5:1" trianthrimide- 2:'2":6:2"-carbazo1e, in a fine state of division,

is added to a vigorously stirredmixtureof 10 parts of diethylformamide, 5 parts of acetonitrile, 3 parts of zinc dust and 0.6 part of methyltriethylammonium chloride. The mixture is stirred under nitrogen at 26 C. for /2 hour. 7 parts of sulphur trioxide in the form of its addition compound with diethylformamide is then added'at 0 C. The mixture is stirred for a further hour'and the product iskthen isolated in the manner described in Example 1.

We claim:

1. The new leuco sulphuric ester dyestufi which in the form of its sodium salt is representedby the formula:

OSOzNa OSO'aNfl NH OSOaNa C C NH OSOaNa OSOaNa OSOsNa 2'; Aprocess for the production of the leuco sulfuric ester dyestuff of 1:1:5:1:1-trianthrimide-2 2 6 2' -carbazole cha'racterir Je'd' "in that the-formation of the leuco sulfuric'esteris" carried out in the presence of a non-vattable' compound selected from the group consisting 'of amideso'f carboxylic' and sulphonic' acids having the for-mula' I R AN/ wherein A represents the acid radical of the amide and R represents a loweralkyl radical.

3. A process as claimed in claim 2, wherein the amide is dimethylformamide.

SAMUEL COFFEY.

DAVID WHYTE FAIRWEATHE'R.

FRANK HAYHURST SLINGER.

REFERENCES CITED The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 999,798 Kalischer Aug. 8, 1911 1,974,866 Hauser et al. Sept. 25-, 1934 2,026,150 Utzinger et a1 Dec. 31, 1935 2,359,864 Linch Oct. 10, 1944 2,403,226 Lecher et'al. July 2, 1946 

2. A PROCESS FOR THE PRODUCTION OF THE LEUCO SULFURIC ESTER DYESTUFF OF 1:1'':5:1:1''''-TRIANTHRIMIDE-2:2'':6:2''''-CARBAZOLE CHARACTERIZED IN THAT THE FORMATION OF THE LEUCO SULFURIC ESTER IS CARRIED OUT IN THE PRESENCE OF A NON-VATTABLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF AMIDES OF CARBOXYLIC AND SULPHONIC ACIDS HAVING THE FORMULA 